JP2010108926A - Lithium manganate powder for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery - Google Patents

Lithium manganate powder for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery Download PDF

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JP2010108926A
JP2010108926A JP2009228223A JP2009228223A JP2010108926A JP 2010108926 A JP2010108926 A JP 2010108926A JP 2009228223 A JP2009228223 A JP 2009228223A JP 2009228223 A JP2009228223 A JP 2009228223A JP 2010108926 A JP2010108926 A JP 2010108926A
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lithium manganate
lithium
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Kazumichi Koga
一路 古賀
Masayuki Uekami
雅之 上神
Hiroaki Masukuni
広明 升國
Kazunobu Matsumoto
和順 松本
Kazutoshi Ishizaki
和俊 石▲崎▼
Hideaki Sadamura
英昭 貞村
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Toda Kogyo Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium manganate having high output power and excellent high-temperature stability. <P>SOLUTION: The lithium manganate particle powder is obtained by mixing and burning a lithium compound, a manganese compound, a Y compound and an A compound and is characterized in that the average secondary particle size (D<SB>50</SB>) is 1-15 μm, (a chemical formula):Li<SB>1+x</SB>Mn<SB>2-x-y</SB>Y<SB>y</SB>O<SB>4</SB>+zA äwherein, Y is at least one of Al and Mg, and A is a sintering assistant element having a melting point of 850 or less (0.03≤x≤0.15, 0≤y≤0.20, and z is 0-2.5 mol% relative to Mn)} is satisfied and a sulfur content of the lithium manganate powder is not more than 100 ppm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、高出力で高温安定性に優れたマンガン酸リチウム粒子粉末を提供する。   The present invention provides a lithium manganate particle powder having high output and excellent high-temperature stability.

近年、ＡＶ機器やパソコン等の電子機器のポータブル化、コードレス化が急速に進んでおり、これらの駆動用電源として小型、軽量で高エネルギー密度を有する二次電池への要求が高くなっている。このような状況下において、充放電電圧が高く、充放電容量も大きいという長所を有するリチウムイオン二次電池が注目されている。   In recent years, electronic devices such as AV devices and personal computers are rapidly becoming portable and cordless, and there is an increasing demand for secondary batteries having a small size, light weight, and high energy density as power sources for driving these devices. Under such circumstances, a lithium ion secondary battery having advantages such as a high charge / discharge voltage and a large charge / discharge capacity has attracted attention.

従来、４Ｖ級の電圧をもつ高エネルギー型のリチウムイオン二次電池に有用な正極活物質としては、スピネル型構造のＬｉＭｎ２Ｏ４、岩塩型構造のＬｉＭｎＯ２、ＬｉＣｏＯ２、ＬｉＣｏ１−ＸＮｉＸＯ２、ＬｉＮｉＯ２等が一般的に知られており、なかでもＬｉＣｏＯ２は高電圧と高容量を有する点で優れているが、コバルト原料の供給量が少ないことによる製造コスト高の問題や廃棄電池の環境安全上の問題を含んでいる。そこで、供給量が多く低コストで環境適性の良いマンガンを原料として作られるスピネル構造型のマンガン酸リチウム粒子粉末（基本組成：ＬｉＭｎ２Ｏ４−以下、同じ−）の研究が盛んに行われている。 Conventionally, as a positive electrode active material useful for a high energy type lithium ion secondary battery having a voltage of 4 V class, spinel type structure LiMn 2 O 4 , rock salt type structure LiMnO 2 , LiCoO 2 , LiCo 1-X Ni X O 2 , LiNiO 2, etc. are generally known. Among them, LiCoO 2 is excellent in that it has a high voltage and a high capacity, but there is a problem of high manufacturing cost due to a small supply amount of cobalt raw material. It includes environmental safety issues of waste batteries. Therefore, research on spinel-structure-type lithium manganate particles (basic composition: LiMn 2 O 4 -hereinafter the same-) made from manganese, which is supplied at a low cost and has good environmental friendliness, has been actively conducted. Yes.

周知の通り、マンガン酸リチウム粒子粉末は、マンガン化合物とリチウム化合物とを所定の割合で混合し、７００〜１０００℃の温度範囲で焼成することによって得ることができる。   As is well known, the lithium manganate particle powder can be obtained by mixing a manganese compound and a lithium compound at a predetermined ratio and firing at a temperature range of 700 to 1000 ° C.

しかしながら、マンガン酸リチウム粒子粉末をリチウムイオン二次電池の正極活物質として用いた場合、高電圧と高エネルギー密度を有するものの、充放電サイクル特性が劣るという問題がある。この原因は、充放電の繰り返しに伴う結晶構造中のリチウムイオンの脱離・挿入挙動によって結晶格子が伸縮して、結晶の体積変化によって格子破壊が生じることや電解液中へマンガンが溶解することとされている。   However, when lithium manganate particle powder is used as a positive electrode active material of a lithium ion secondary battery, although it has a high voltage and a high energy density, there is a problem that charge / discharge cycle characteristics are inferior. This is due to the fact that the crystal lattice expands and contracts due to the lithium ion desorption / insertion behavior in the crystal structure with repeated charge and discharge, and that the lattice breaks due to the volume change of the crystal and that manganese dissolves in the electrolyte. It is said that.

マンガン酸リチウム粒子粉末を用いたリチウムイオン二次電池にあっては、充放電の繰り返しによる充放電容量の劣化を抑制し、特に高温、低温での充放電サイクル特性を向上させることが現在最も要求されている。   In lithium ion secondary batteries using lithium manganate particles, the most current demand is to suppress deterioration of charge / discharge capacity due to repeated charge / discharge and to improve charge / discharge cycle characteristics at high and low temperatures. Has been.

充放電サイクル特性を向上させるためには、マンガン酸リチウム粒子粉末からなる正極活物質が充填性に優れ、適度な大きさを有すること、更にマンガン溶出を抑制することが必要である。その手段としては、マンガン酸リチウム粒子の粒子径及び粒度分布を制御する方法、焼成温度を制御して高結晶のマンガン酸リチウム粒子粉末を得る方法、異種元素を添加して結晶の結合力を強化する方法、表面処理を行うことや、添加物を混ぜることでマンガンの溶出を抑制する方法等が行われている。   In order to improve the charge / discharge cycle characteristics, it is necessary that the positive electrode active material made of lithium manganate particle powder is excellent in filling property, has an appropriate size, and further suppresses elution of manganese. As the means, a method of controlling the particle size and particle size distribution of lithium manganate particles, a method of obtaining a highly crystalline lithium manganate particle powder by controlling the firing temperature, and strengthening the bonding power of crystals by adding different elements And a method of suppressing the elution of manganese by mixing an additive and a surface treatment.

これまで、マンガン酸リチウム粒子粉末にアルミニウムを含有させることが知られている（特許文献１）。また、マンガン酸リチウムを作製する際に、焼結助剤として酸化ホウ素、ホウ酸、ホウ酸リチウム、ホウ酸アンモニウム等を添加することで、焼結助剤効果を得られることが知られている（特許文献２）。また、マンガン酸リチウムの硫黄含有量を低減することが知られている（特許文献３）。   Until now, it is known that lithium manganate particle powder contains aluminum (Patent Document 1). In addition, it is known that a sintering aid effect can be obtained by adding boron oxide, boric acid, lithium borate, ammonium borate or the like as a sintering aid when producing lithium manganate. (Patent Document 2). It is also known to reduce the sulfur content of lithium manganate (Patent Document 3).

特開２００１−１４６４２５号公報JP 2001-146425 A 特開２００１−４８５４７号公報JP 2001-48547 A 特開２００２−１９８０４７号公報JP 2002-198047 A

非水電解質二次電池用の正極活物質として出力特性と高温特性を改善するマンガン酸リチウムが、現在最も要求されているところであるが、未だ必要十分な要求を満たす材料や製造方法が得られていない。   As the positive electrode active material for nonaqueous electrolyte secondary batteries, lithium manganate, which improves output characteristics and high-temperature characteristics, is currently the most demanded, but materials and manufacturing methods that satisfy the necessary and sufficient requirements have not yet been obtained. Absent.

即ち、前記特許文献１〜３には、それぞれ、金属元素をマンガンの一部をＡｌ元素で置換したマンガン酸リチウム、焼結助剤を少量添加したマンガン酸リチウム、硫黄量を低減したマンガン酸リチウムが記載されているが、電池の高温特性が満足するものではなく実用的にまだ不十分であった。   That is, in Patent Documents 1 to 3, lithium metal manganate in which a part of manganese is replaced with Al element, lithium manganate to which a small amount of sintering aid is added, and lithium manganate in which the amount of sulfur is reduced. However, the high-temperature characteristics of the battery are not satisfactory and are still insufficient in practice.

そこで、本発明では、高出力で高温安定性（高温保存特性）に優れたマンガン酸リチウムを提供することを技術的課題とするものである。   Therefore, the present invention has a technical problem to provide lithium manganate having high output and high temperature stability (high temperature storage characteristics).

前記技術的課題は、次の通りの本発明によって達成できる。   The technical problem can be achieved by the present invention as follows.

即ち、本発明は、化学式１のマンガン酸リチウム粒子粉末において、硫黄含有量が１〜１００ｐｐｍであり、平均二次粒子径（Ｄ５０）が１μｍ〜１５μｍであり、且つ、該マンガン酸リチウム粒子粉末を正極活物質として用いた二次電池の電池測定において、高温サイクル維持率が９２％以上、容量回復率が９５％以上であることを特徴とするマンガン酸リチウム粒子粉末である（本発明１）。
（化学式１）
Ｌｉ１＋ｘＭｎ２−ｘ−ｙＹｙＯ４＋ｚＡ
Ｙ＝Ａｌ、Ｍｇの少なくとも１種
Ａ＝融点が８５０℃以下である焼結助剤元素
（０．０３≦ｘ≦０．１５、０≦ｙ≦０．２０、ｚはＭｎに対して０〜２．５ｍｏｌ％） That is, the present invention relates to a lithium manganate particle powder of Formula 1, wherein the sulfur content is 1 to 100 ppm, the average secondary particle diameter (D 50 ) is 1 μm to 15 μm, and the lithium manganate particle powder A lithium manganate particle powder characterized by having a high-temperature cycle maintenance rate of 92% or more and a capacity recovery rate of 95% or more in a battery measurement of a secondary battery using a cathode as a positive electrode active material (Invention 1) .
(Chemical formula 1)
Li 1 + x Mn 2-xy Y y O 4 + zA
Y = Al, at least one of Mg A = Sintering aid element having a melting point of 850 ° C. or lower (0.03 ≦ x ≦ 0.15, 0 ≦ y ≦ 0.20, z is 0 to Mn) 2.5 mol%)

また、本発明は、格子定数が０．８１８〜０．８２２ｎｍである本発明１記載のマンガン酸リチウム粒子粉末である（本発明２）。   Moreover, this invention is a lithium manganate particle powder of this invention 1 whose lattice constant is 0.818-0.822 nm (this invention 2).

また、本発明は、前記マンガン酸リチウム粒子粉末を正極活物質として用いた二次電池の充放電容量を測定した場合に、初期の放電容量が８０ｍＡｈ／ｇ以上、１２０ｍＡｈ／ｇ以下である本発明１又は２に記載のマンガン酸リチウム粒子粉末である（本発明３）。   In addition, the present invention provides an initial discharge capacity of 80 mAh / g or more and 120 mAh / g or less when a charge / discharge capacity of a secondary battery using the lithium manganate particle powder as a positive electrode active material is measured. The lithium manganate particle powder according to 1 or 2 (Invention 3).

また、本発明は、Ｍｎ３Ｏ４からなる酸化マンガン、Ｙ元素化合物及びリチウム化合物を混合し、８００℃〜１０５０℃で焼成することを特徴とする本発明１〜３のいずれかに記載のマンガン酸リチウム粒子粉末の製造方法である（本発明４）。 Further, the present invention, Mn 3 O of four manganese oxide, a mixture of Y element compound and a lithium compound, as claimed in any one of the present invention 1 to 3 and firing at 800 ° C. to 1050 ° C. Manganese This is a method for producing lithium acid particle powder (Invention 4).

また、本発明は、本発明４記載のマンガン酸リチウム粒子粉末の製造方法において、酸化マンガンの硫黄含有量が１〜６０ｐｐｍであるマンガン酸リチウム粒子粉末の製造方法である（本発明５）。   Moreover, this invention is a manufacturing method of the lithium manganate particle powder whose sulfur content of manganese oxide is 1-60 ppm in the manufacturing method of the lithium manganate particle powder of this invention 4 (this invention 5).

また、本発明は、本発明４記載のマンガン酸リチウム粒子粉末の製造方法において、酸化マンガンの平均一次粒子径が０．５μｍ以上であるマンガン酸リチウム粒子粉末の製造方法である（本発明６）。   The present invention also relates to a method for producing lithium manganate particles having an average primary particle size of manganese oxide of 0.5 μm or more in the method for producing lithium manganate particles according to the present invention 4 (Invention 6). .

また、本発明は、本発明１〜３のいずれかに記載のマンガン酸リチウム粒子粉末を正極活物質またはその一部として用いた非水電解液二次電池である（本発明７）。   Moreover, this invention is a non-aqueous-electrolyte secondary battery using the lithium manganate particle powder in any one of this invention 1-3 as a positive electrode active material or its part (this invention 7).

本発明に係るマンガン酸リチウム粒子粉末は、高出力であり、高温安定性に優れているので、非水電解質二次電池用の正極活物質として好適である。   Since the lithium manganate particle powder according to the present invention has high output and excellent high-temperature stability, it is suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery.

実施例１で得られたマンガン酸リチウムのＳＥＭ像SEM image of lithium manganate obtained in Example 1 硫黄含有量と高温サイクル維持率の関係を示した図Figure showing the relationship between sulfur content and high temperature cycle retention 硫黄含有量と容量回復率の関係を示した図Diagram showing the relationship between sulfur content and capacity recovery rate

本発明の構成をより詳しく説明すれば次の通りである。   The configuration of the present invention will be described in more detail as follows.

先ず、本発明に係る非水電解質二次電池用マンガン酸リチウム粒子粉末について述べる。   First, the lithium manganate particle powder for nonaqueous electrolyte secondary batteries according to the present invention will be described.

本発明に係るマンガン酸リチウム粒子粉末は、硫黄含有量が１００ｐｐｍ以下であり、且つ、電池測定において高温サイクル維持率が９２％以上、容量回復率が９５％以上であり、また、平均二次粒子径（Ｄ５０）が１μｍ〜１５μｍである。 The lithium manganate particle powder according to the present invention has a sulfur content of 100 ppm or less, a high temperature cycle retention rate of 92% or more, a capacity recovery rate of 95% or more in battery measurement, and an average secondary particle. diameter (D 50) is 1Myuemu～15myuemu.

本発明に係るマンガン酸リチウム粒子粉末の化学式は、Ｌｉ１＋ｘＭｎ２−ｘ−ｙＹｙＯ４＋ｚＡであり、ＹはＡｌ／Ｍｇの少なくとも１種である。このうち、ｘは０．０３〜０．１５であり、ｙは０〜０．２０、ｚはＭｎに対して０〜２．５ｍｏｌ％である。
ｘが０．０３未満の場合、容量は高くなるが高温特性が著しく低下する。０．１５を超える場合には高温特性は改善されるが容量が著しく低下したりＬｉリッチ相が生成し抵抗上昇の原因になる。より好ましくは０．０５〜０．１５である。
ｙが０．２０を超える場合には容量低下が大きくなるために実用的でない。好ましくは０．０１〜０．１８であり、より好ましくは０．０５〜０．１５である。
ｚがＭｎに対し２．５ｍｏｌ％を超える場合、凝集効果若しくは焼結防止効果が強すぎ、高温特性を損ねる原因となる。より好ましくは０．０１〜２．０ｍｏｌ％であり、更により好ましくは０．１〜１．８ｍｏｌ％である。 The chemical formula of the lithium manganate particles according to the present invention is Li 1 + x Mn 2−xy Y y O 4 + zA, and Y is at least one of Al / Mg. Among these, x is 0.03-0.15, y is 0-0.20, z is 0-2.5 mol% with respect to Mn.
When x is less than 0.03, the capacity is increased, but the high temperature characteristics are remarkably deteriorated. When it exceeds 0.15, the high temperature characteristics are improved, but the capacity is remarkably lowered or a Li-rich phase is generated, which causes an increase in resistance. More preferably, it is 0.05-0.15.
When y exceeds 0.20, the capacity drop is increased, which is not practical. Preferably it is 0.01-0.18, More preferably, it is 0.05-0.15.
When z exceeds 2.5 mol% with respect to Mn, the aggregation effect or the sintering preventing effect is too strong, which causes the high temperature characteristics to be impaired. More preferably, it is 0.01-2.0 mol%, More preferably, it is 0.1-1.8 mol%.

本発明に係るマンガン酸リチウム粒子粉末の硫黄含有量は１００ｐｐｍ以下である。１００ｐｐｍを超える場合は、焼成時に局所的に焼結が進み、偏在的に凝集が発生してしまい、焼成物の硬柔が発生してしまう。また、電池セルにしたときに、例えばＦｅなどの不純物と硫黄化合物を形成し、電池のショートの原因となってしまう。且つ、高温保存時にＭｎ溶出を促す効果が見られ、高温時の特性が不安定になる。好ましくは８０ｐｐｍ以下であり、より好ましくは１〜６０ｐｐｍである。   The sulfur content of the lithium manganate particles according to the present invention is 100 ppm or less. When it exceeds 100 ppm, sintering proceeds locally at the time of firing, and agglomeration occurs unevenly, resulting in the softness of the fired product. Moreover, when it is set as a battery cell, impurities, such as Fe, and a sulfur compound will be formed, for example, and it will cause a short circuit of a battery. In addition, the effect of promoting Mn elution during high temperature storage is observed, and the characteristics at high temperature become unstable. Preferably it is 80 ppm or less, More preferably, it is 1-60 ppm.

本発明においては、硫黄化合物の含有量が低減されたマンガン原料、硫酸塩が低減されたＬｉ化合物、Ｙ元素の化合物及びＡ元素の化合物を乾式にて混合することで、硫黄化合物が低減されたマンガン酸リチウム粒子粉末を得ることができる。   In the present invention, the sulfur compound was reduced by dry mixing the manganese raw material with reduced sulfur compound content, the Li compound with reduced sulfate, the Y element compound and the A element compound. Lithium manganate particle powder can be obtained.

本発明に係るマンガン酸リチウム粒子粉末の格子定数は０．８１８〜０．８２２ｎｍが好ましい。格子定数が０．８１８ｎｍ未満の場合には、容量が低下する。０．８２２ｎｍを超える場合には、安定性が低下する。より好ましくは０．８１９〜０．８２１ｎｍである。   The lattice constant of the lithium manganate particles according to the present invention is preferably 0.818 to 0.822 nm. When the lattice constant is less than 0.818 nm, the capacity decreases. When it exceeds 0.822 nm, the stability is lowered. More preferably, it is 0.819 to 0.821 nm.

本発明に係るマンガン酸リチウム粒子粉末の平均一次粒子径は０．５〜１０μｍが好ましい。一次粒子径が０．５μｍ未満の場合には、安定性が低下する。１０μｍを超える場合には、出力が低下する。より好ましくは１．０〜８．０μｍである。   The average primary particle diameter of the lithium manganate particles according to the present invention is preferably 0.5 to 10 μm. When the primary particle diameter is less than 0.5 μm, the stability is lowered. When it exceeds 10 μm, the output decreases. More preferably, it is 1.0-8.0 micrometers.

本発明に係るマンガン酸リチウム粒子粉末の平均二次粒子径（Ｄ５０）は１．０μｍ以上、１５μｍ以下である。平均二次粒子径が１μｍ未満の場合には、安定性が低下する。平均二次粒子径（Ｄ５０）が１５μｍを超える場合には、出力が低下する。より好ましくは２．０〜１２．０μｍである。 The average secondary particle diameter (D 50 ) of the lithium manganate particles according to the present invention is 1.0 μm or more and 15 μm or less. When the average secondary particle diameter is less than 1 μm, the stability is lowered. When the average secondary particle diameter (D 50 ) exceeds 15 μm, the output decreases. More preferably, it is 2.0-12.0 micrometers.

本発明に係るマンガン酸リチウム一次粒子は、実質的に単結晶からなることが好ましい。多結晶体である場合には、格子不整合面が多数存在するためにリチウムの脱挿入に対して抵抗成分となり、出力がとりにくくなる場合がある。   The primary lithium manganate particles according to the present invention are preferably substantially composed of a single crystal. In the case of a polycrystal, since there are many lattice mismatch planes, it becomes a resistance component against lithium insertion and removal, and it may be difficult to obtain an output.

本発明に係るマンガン酸リチウム粒子粉末のＢＥＴ比表面積は、１．０ｍ２／ｇ以下が好ましく、より好ましくは０．１〜０．８ｍ２／ｇである。 BET specific surface area of the lithium manganate particles according to the present invention is preferably from 1.0 m 2 / g or less, more preferably 0.1~0.8m 2 / g.

次に、本発明に係るマンガン酸リチウム粒子粉末の製造法について述べる。   Next, a method for producing lithium manganate particles according to the present invention will be described.

本発明に係るマンガン酸リチウム粒子粉末は、Ｍｎ３Ｏ４からなる酸化マンガンとリチウム化合物、必要により、Ｙ元素化合物及び／又は融点が８５０℃以下である焼結助剤を混合し、８００℃〜１０５０℃で焼成して得ることができる。 The lithium manganate particle powder according to the present invention is a mixture of manganese oxide composed of Mn 3 O 4 and a lithium compound, and if necessary, a Y element compound and / or a sintering aid having a melting point of 850 ° C. or less. It can be obtained by firing at 1050 ° C.

本発明に係るマンガン酸リチウム粒子粉末の出発原料であるマンガン化合物は、Ｍｎ３Ｏ４が好ましい。電解ＭｎＯ２などと異なり、湿式反応により不純物を下げて作製することができ、且つ、実質的に単結晶である粒子を作製することができる。 The manganese compound that is the starting material of the lithium manganate particles according to the present invention is preferably Mn 3 O 4 . Unlike electrolytic MnO 2 or the like, it can be produced by reducing impurities by a wet reaction, and particles that are substantially single crystals can be produced.

具体的には、（１）マンガン塩水溶液とアルカリ水溶液とを反応させマンガン水酸化物を含有する水懸濁液とし、次いで、６０〜１００℃の温度範囲で酸化反応を行って四酸化三マンガン核粒子を得る一次反応を行い、該一次反応後の反応溶液にマンガン塩水溶液を添加した後、酸化反応を行って前記四酸化三マンガン核粒子の成長反応を行う二次反応によって四酸化三マンガン粒子を得る製造法において、一次反応のマンガン濃度を１．５ｍｏｌ／Ｌ以下にするとともに、二次反応のマンガン添加量を一次反応のマンガン濃度の等モル以下にする製造法、（２）前記四酸化三マンガン粒子を得る製造法において、一次反応終了後の反応溶液を非酸化性雰囲気に切り替えた後、マンガン塩水溶液を添加し、次いで、３時間以内の熟成を行う製造法、（３）前記四酸化三マンガン粒子を得る製造法において、一次反応及び／又は二次反応中にマンガンに対して０．５モル％以下の有機還元剤を存在させる製造法、（４）前記四酸化三マンガン粒子を得る製造法において、過剰アルカリ濃度を１．０〜５ｍｏｌ／Ｌとして四酸化三マンガン粒子粉末を得る製造法などである。   Specifically, (1) an aqueous manganese salt solution and an alkaline aqueous solution are reacted to form an aqueous suspension containing manganese hydroxide, and then an oxidation reaction is performed in a temperature range of 60 to 100 ° C. to obtain trimanganese tetraoxide. A primary reaction for obtaining core particles is performed, and an aqueous manganese salt solution is added to the reaction solution after the primary reaction, and then an oxidation reaction is performed to perform a growth reaction of the trimanganese tetroxide core particles. In the production method for obtaining particles, the production method in which the manganese concentration in the primary reaction is 1.5 mol / L or less and the manganese addition amount in the secondary reaction is equal to or less than the equimolar amount of the manganese concentration in the primary reaction, (2) In the production method for obtaining trimanganese oxide particles, the reaction solution after completion of the primary reaction is switched to a non-oxidizing atmosphere, an aqueous manganese salt solution is added, and then the aging is performed for 3 hours or less. (3) In the production method for obtaining the trimanganese tetroxide particles, a production method in which an organic reducing agent is present in an amount of 0.5 mol% or less based on manganese during the primary reaction and / or the secondary reaction, (4) Examples of the production method for obtaining the trimanganese tetroxide particles include a production method for obtaining a trimanganese tetroxide particle powder with an excess alkali concentration of 1.0 to 5 mol / L.

本発明における四三酸化マンガン（Ｍｎ３Ｏ４）は、平均二次粒子径（Ｄ５０）が１．０〜８．０μｍ、平均一次粒子径が０．５μｍ以上、より好ましくは１．０〜８．０μｍであって、ＢＥＴ比表面積０．５〜１５ｍ２／ｇであり、硫黄含有量が１〜６０ｐｐｍ、より好ましくは１〜５０ｐｐｍであることが好ましい。また、四三酸化マンガン（Ｍｎ３Ｏ４）は実質的に単結晶であることが好ましい。 The trimanganese tetraoxide (Mn 3 O 4 ) in the present invention has an average secondary particle diameter (D 50 ) of 1.0 to 8.0 μm, an average primary particle diameter of 0.5 μm or more, more preferably 1.0 to It is 8.0 μm, the BET specific surface area is 0.5 to 15 m 2 / g, and the sulfur content is preferably 1 to 60 ppm, more preferably 1 to 50 ppm. Further, it is preferable that trimanganese tetraoxide (Mn 3 O 4 ) is substantially a single crystal.

本発明に係るマンガン酸リチウム粒子粉末のＹ元素（Ａｌ／Ｍｇ）は、Ｙ元素化合物を微粒化させることでマンガン化合物との反応性を増加させることができ、その結果、粒子内部に均一に分散させることができる。Ｙ元素がマンガン酸リチウム粒子粉末中に偏在している場合には安定性が低下することがある。Ｙ元素化合物は、平均二次粒子径（Ｄ５０）が１．０〜２０μｍとなるように粒子径を制御することが好ましい。 The Y element (Al / Mg) in the lithium manganate particles according to the present invention can increase the reactivity with the manganese compound by atomizing the Y element compound, and as a result, uniformly dispersed inside the particles. Can be made. When the Y element is unevenly distributed in the lithium manganate particle powder, the stability may be lowered. It is preferable to control the particle diameter of the Y element compound so that the average secondary particle diameter (D 50 ) is 1.0 to 20 μm.

本発明では融点が８００℃以下である焼結助剤を添加して焼成を行ってもよい。より好ましくは融点が６００℃以下の焼結助剤である。融点が８００℃以下である焼結助剤としてはホウ素化合物が好ましい。ホウ素化合物は、ホウ酸、四ホウ酸リチウム、酸化ホウ素、ホウ酸アンモニウムなどが挙げられる。特に良好なのはホウ酸を使用した場合である。   In the present invention, sintering may be performed by adding a sintering aid having a melting point of 800 ° C. or less. More preferred is a sintering aid having a melting point of 600 ° C. or lower. As a sintering aid having a melting point of 800 ° C. or lower, a boron compound is preferable. Examples of the boron compound include boric acid, lithium tetraborate, boron oxide, and ammonium borate. Particularly good is when boric acid is used.

マンガン酸化物とリチウム化合物、必要により、Ｙ元素化合物及び／又はＡ元素化合物を、所定の比率で混合した後、焼成固相反応によりマンガン酸リチウムを得ることができるが、焼成温度は８００℃以上でなくてはならない。８００℃未満ではＹ元素化合物が粒子内部で均一に分布した状態を得ることはできない。
例えば、前出特許文献１（特開２００１−１４６４２５号公報）では、粒子外観のＥＰＭＡ分析により、Ａｌの均質状態を検証しているが、Ａｌが粒子表面のみに局在していてもこのような結果が得られるが、実際の出力を測定すると、抵抗が大きく、電流を取り出しにくいということが発生する。好ましくは８５０℃〜１０５０℃の温度範囲で焼成する。 Manganese oxide and lithium compound, and if necessary, Y element compound and / or A element compound are mixed at a predetermined ratio, and then lithium manganate can be obtained by a firing solid phase reaction. It must be. If it is less than 800 degreeC, the state in which the Y element compound was uniformly distributed inside the particle cannot be obtained.
For example, in the above-mentioned patent document 1 (Japanese Patent Laid-Open No. 2001-146425), the homogeneity state of Al is verified by EPMA analysis of the particle appearance, but even if Al is localized only on the particle surface, However, when the actual output is measured, the resistance is large and it is difficult to extract the current. Preferably, the baking is performed at a temperature range of 850 ° C to 1050 ° C.

次に、本発明に係る非水電解質二次電池用マンガン酸リチウム粒子粉末からなる正極活物質を用いた正極について述べる。   Next, the positive electrode using the positive electrode active material which consists of lithium manganate particle powder for nonaqueous electrolyte secondary batteries which concerns on this invention is described.

本発明に係る正極活物質を用いて正極を製造する場合には、常法に従って、導電剤と結着剤とを添加混合する。導電剤としてはアセチレンブラック、カーボンブラック、黒鉛等が好ましく、結着剤としてはポリテトラフルオロエチレン、ポリフッ化ビニリデン等が好ましい。   When a positive electrode is produced using the positive electrode active material according to the present invention, a conductive agent and a binder are added and mixed according to a conventional method. As the conductive agent, acetylene black, carbon black, graphite and the like are preferable, and as the binder, polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.

本発明に係る正極活物質を用いて製造される二次電池は、前記正極、負極及び電解質から構成される。   The secondary battery manufactured using the positive electrode active material according to the present invention includes the positive electrode, the negative electrode, and an electrolyte.

負極活物質としては、リチウム金属、リチウム／アルミニウム合金、リチウム／スズ合金、グラファイトや黒鉛等を用いることができる。   As the negative electrode active material, lithium metal, lithium / aluminum alloy, lithium / tin alloy, graphite, graphite, or the like can be used.

また、電解液の溶媒としては、炭酸エチレンと炭酸ジエチルの組み合わせ以外に、炭酸プロピレン、炭酸ジメチル等のカーボネート類や、ジメトキシエタン等のエーテル類の少なくとも１種類を含む有機溶媒を用いることができる。   In addition to the combination of ethylene carbonate and diethyl carbonate, an organic solvent containing at least one of carbonates such as propylene carbonate and dimethyl carbonate and ethers such as dimethoxyethane can be used as the solvent for the electrolytic solution.

さらに、電解質としては、六フッ化リン酸リチウム以外に、過塩素酸リチウム、四フッ化ホウ酸リチウム等のリチウム塩の少なくとも１種類を上記溶媒に溶解して用いることができる。   Further, as the electrolyte, in addition to lithium hexafluorophosphate, at least one lithium salt such as lithium perchlorate and lithium tetrafluoroborate can be dissolved in the above solvent and used.

本発明に係るマンガン酸リチウム粒子粉末を用いて製造した二次電池は、初期の放電容量が８０〜１２０ｍＡｈ／ｇであり、レート特性は、８０％以上が好ましく、より好ましくは９０％以上であり、高温サイクル維持率が９２％以上であり、容量回復率が９５％以上である。   The secondary battery manufactured using the lithium manganate particles according to the present invention has an initial discharge capacity of 80 to 120 mAh / g, and the rate characteristic is preferably 80% or more, more preferably 90% or more. The high-temperature cycle maintenance rate is 92% or more, and the capacity recovery rate is 95% or more.

本発明の代表的な実施の形態は次の通りである。   A typical embodiment of the present invention is as follows.

平均二次粒子径（Ｄ５０）はレーザー式粒度分布測定装置マイクロトラックＨＲＡ［日機装（株）製］を用いて湿式レーザー法で測定した体積基準の平均粒子径である。 The average secondary particle size (D 50 ) is a volume-based average particle size measured by a wet laser method using a laser type particle size distribution measuring device Microtrac HRA [manufactured by Nikkiso Co., Ltd.].

平均一次粒子径は、エネルギー分散型Ｘ線分析装置付き走査電子顕微鏡ＳＥＭ−ＥＤＸ［（株）日立ハイテクノロジーズ製］を用いて観察し、平均値を読み取った。   The average primary particle size was observed using a scanning electron microscope SEM-EDX with an energy dispersive X-ray analyzer [manufactured by Hitachi High-Technologies Corporation], and the average value was read.

元素の存在状態はエネルギー分散型Ｘ線分析装置付き走査電子顕微鏡ＳＥＭ−ＥＤＸ［（株）日立ハイテクノロジーズ製］を用いて観察した。   The presence state of the elements was observed using a scanning electron microscope SEM-EDX with an energy dispersive X-ray analyzer [manufactured by Hitachi High-Technologies Corporation].

組成は、０．２ｇの試料を２０％塩酸溶液２５ｍｌの溶液で加熱溶解させ、冷却後１００ｍｌメスフラスコに純水を入れ調整液を作製し、測定にはＩＣＡＰ［ＳＰＳ−４０００ セイコー電子工業（株）製］を用いて各元素を定量して決定した。   The composition was prepared by dissolving 0.2 g of a sample with 25 ml of a 20% hydrochloric acid solution and cooling to prepare pure liquid in a 100 ml volumetric flask. For measurement, ICAP [SPS-4000 Seiko Electronics Co., Ltd. ))] Was used to quantify each element.

硫黄含有量は、５ｇの試料を炭素・硫黄測定装置［ＥＭＩＡ−５２０ＦＡ （株）堀場製作所製］の燃焼炉で酸素気流中にて燃焼させ測定された量である。   The sulfur content is an amount measured by burning a 5 g sample in a combustion furnace of a carbon / sulfur measuring apparatus [EMIA-520FA, manufactured by Horiba, Ltd.] in an oxygen stream.

試料のＸ線回折は、株式会社リガク製 ＲＡＤ−ＩＩＡを用いて測定した。   The X-ray diffraction of the sample was measured using RAD-IIA manufactured by Rigaku Corporation.

格子定数は、前記粉末Ｘ線回折結果からリートベルト法で算出した。   The lattice constant was calculated by the Rietveld method from the powder X-ray diffraction results.

作製した粒子が単結晶か否かの確認は、粒子断面についてＥＢＳＤ解析を行い配向面を観察した。   To confirm whether the produced particles are single crystals, EBSD analysis was performed on the cross section of the particles, and the orientation plane was observed.

マンガン酸リチウム粒子粉末を用いてコインセルによる初期充放電特性及び高温保存特性評価を行った。
まず、正極活物質としてＬｉ−Ｍｎ複合酸化物を９２重量％、導電材としてアセチレンブラックを２．５重量％及びグラファイトを２．５重量％、バインダーとしてＮ−メチル−２−ピロリドンに溶解したポリフッ化ビニリデン３重量％とを混合した後、Ａｌ金属箔に塗布し１１０℃にて乾燥した。このシートを１６ｍｍφに打ち抜いた後、１ｔ／ｃｍ２で圧着し、電極厚みを５０μｍとした物を正極に用いた。負極は１６ｍｍφに打ち抜いた金属リチウムとし、電解液は１ｍｏｌ／ｌのＬｉＰＦ６を溶解したＥＣとＤＥＣを体積比で３：７で混合した溶液を用いてＣＲ２０３２型コインセルを作製した。
初期充放電特性は、２５℃で充電は４．３Ｖまで０．１Ｃの電流密度にて行った後、９０分間定電圧充電を行い、放電を３．０Ｖまで０．１Ｃの電流密度にて実施し、その時の初期充電容量、初期放電容量及び初期充放電効率を測定した。 The initial charge / discharge characteristics and high-temperature storage characteristics of the coin cell were evaluated using lithium manganate particles.
First, 92% by weight of a Li—Mn composite oxide as a positive electrode active material, 2.5% by weight of acetylene black and 2.5% by weight of graphite as a conductive material, and a polyfluoride dissolved in N-methyl-2-pyrrolidone as a binder. After mixing with 3% by weight of vinylidene chloride, it was applied to an Al metal foil and dried at 110 ° C. The sheet was punched to 16 mmφ, and then pressure-bonded at 1 t / cm 2 to make the electrode thickness 50 μm. The negative electrode was metallic lithium blanked into diameter of 16 mm, the electrolytic solution 3 EC and DEC in which LiPF 6 was dissolved in 1 mol / l at a volume ratio of: was prepared a coin cell of a CR2032 type using a mixed solution of 7.
The initial charge / discharge characteristics were as follows: charging at 25 ° C. and charging at a current density of 0.1 C up to 4.3 V, followed by constant voltage charging for 90 minutes and discharging at a current density of 0.1 C up to 3.0 V The initial charge capacity, initial discharge capacity, and initial charge / discharge efficiency at that time were measured.

また、高温時特性として、容量回復率については、１サイクル充放電後（放電容量ａ）、０．１Ｃで充電深度５０％まで充電を行ったのちに、６０℃で１週間保存した後、０．１Ｃで３．０Ｖまで放電し、更に０．１Ｃで充放電（放電容量ｂ）を行ない、「容量回復率」（＝１００×ｂ／ａ）とした。
また、「高温サイクル維持率」については、６０℃恒温槽で電圧範囲３．０〜４．３Ｖとして、１サイクル目、１１サイクル目、２１サイクル目、３１サイクル目を０．１Ｃの電流密度で充放電（充電は定電流−９０分定電圧充電）を行い、その他のサイクルは、１Ｃの電流密度で充放電（充電は定電流−９０分定電圧充電）を繰り返し、初回放電容量ｃに対する３１サイクル目の放電容量ｄの割合（＝１００×ｄ／ｃ）とした。
また、２５℃で電圧範囲３．０〜４．３Ｖとして、充電は０．１Ｃ（４．３Ｖで９０分の定電圧充電）、放電は０．１Ｃ・０．２Ｃ・０．５Ｃ・１Ｃ・２Ｃ・５Ｃと充放電を実施した。このとき（５Ｃ放電容量／０．１Ｃ放電容量）×１００の値を「レート特性」とした。 In addition, as a high temperature characteristic, the capacity recovery rate was 0 after charging for 1 cycle after charging / discharging (discharge capacity a), charging at 0.1 C to a charge depth of 50%, and storing at 60 ° C. for 1 week. The battery was discharged to 3.0 V at 1 C, and further charged and discharged (discharge capacity b) at 0.1 C to obtain a “capacity recovery rate” (= 100 × b / a).
Regarding the “high temperature cycle maintenance rate”, the voltage range is 3.0 to 4.3 V in a constant temperature bath at 60 ° C., and the current density of the first cycle, the 11th cycle, the 21st cycle, and the 31st cycle is 0.1 C. Charging / discharging (charging is constant current-90 minutes constant voltage charging) is performed, and in other cycles, charging / discharging (charging is constant current-90 minutes constant voltage charging) is repeated at a current density of 1 C, and 31 for the initial discharge capacity c. The ratio of the discharge capacity d at the cycle (= 100 × d / c) was used.
In addition, the voltage range is 3.0 to 4.3 V at 25 ° C., the charging is 0.1 C (constant voltage charging at 4.3 V for 90 minutes), and the discharging is 0.1 C · 0.2 C · 0.5 C · 1 C · Charging / discharging was performed with 2C / 5C. At this time, the value of (5C discharge capacity / 0.1C discharge capacity) × 100 was defined as “rate characteristic”.

実施例１ ＜マンガン酸リチウム粒子粉末の製造＞
窒素通気のもと、３．５モルの水酸化ナトリウムに０．５モルの硫酸マンガンを加え全量を１Ｌとし、得られた水酸化マンガンを９０℃で１時間熟成させた。熟成後、空気を通気させ９０℃で酸化させ、水洗、乾燥後、酸化マンガン粒子粉末を得た。 Example 1 <Production of Lithium Manganate Particle Powder>
Under nitrogen aeration, 0.5 mol of manganese sulfate was added to 3.5 mol of sodium hydroxide to make the total amount 1 L, and the obtained manganese hydroxide was aged at 90 ° C. for 1 hour. After aging, air was passed through, oxidized at 90 ° C., washed with water and dried to obtain manganese oxide particles.

得られた酸化マンガン粒子粉末はＭｎ３Ｏ４であり、粒子形状は粒状であり、平均一次粒子径４．８μｍ、ＢＥＴ比表面積が０．６ｍ２／ｇであった。また、硫黄含有量は８ｐｐｍであった。 The obtained manganese oxide particle powder was Mn 3 O 4 , the particle shape was granular, the average primary particle size was 4.8 μm, and the BET specific surface area was 0.6 m 2 / g. The sulfur content was 8 ppm.

前記Ｍｎ３Ｏ４粒子粉末、炭酸リチウム及び水酸化アルミニウムをＬｉ：Ｍｎ：Ａｌ＝１．０７２：１．８２８：０．１０の割合になるように１時間混合し、均一な混合物を得た。水酸化アルミニウムは粉砕して平均二次粒子径（Ｄ５０）が１０μｍであるものを用いた。得られた混合物５０ｇをアルミナるつぼに入れ、９６０℃、空気雰囲気で３時間保持してマンガン酸リチウム粒子粉末を得た。 The Mn 3 O 4 particle powder, lithium carbonate and aluminum hydroxide were mixed for 1 hour at a ratio of Li: Mn: Al = 1.72: 1.828: 0.10 to obtain a uniform mixture. Aluminum hydroxide having an average secondary particle diameter (D 50 ) of 10 μm was pulverized. 50 g of the obtained mixture was put in an alumina crucible and kept at 960 ° C. in an air atmosphere for 3 hours to obtain lithium manganate particles.

得られたマンガン酸リチウム粒子粉末は、組成をＬｉ１＋ｘＭｎ２−ｘ−ｙＯ４とした場合に、ｘが０．０７２、ｙが０．１０であり、平均一次粒子径が５．０μｍであり、平均二次粒子径（Ｄ５０）が７．３μｍであり、ＢＥＴ比表面積値が０．４５ｍ２／ｇ、格子定数は０．８１９８ｎｍ、硫黄含有量は１２ｐｐｍであった。 The obtained lithium manganate particle powder has a composition of Li 1 + x Mn 2-xy O 4 , x is 0.072, y is 0.10, and the average primary particle size is 5.0 μm. The average secondary particle diameter (D 50 ) was 7.3 μm, the BET specific surface area value was 0.45 m 2 / g, the lattice constant was 0.8198 nm, and the sulfur content was 12 ppm.

ここで得たマンガン酸リチウム粒子粉末からなる正極活物質を用いて作製したコイン型電池は、初期放電容量が１０５ｍＡｈ／ｇであった。６０℃、１週間保存後の容量回復率は９６％であり、高温サイクル維持率は９５％で、レート特性は９６％であった。   The coin-type battery produced using the positive electrode active material made of the lithium manganate particles obtained here had an initial discharge capacity of 105 mAh / g. The capacity recovery rate after storage at 60 ° C. for 1 week was 96%, the high-temperature cycle maintenance rate was 95%, and the rate characteristics were 96%.

実施例２
酸化マンガンの種類を替えて、表１に示す組成となるようにＭｎ３Ｏ４粒子粉末、炭酸リチウム、水酸化アルミニウムと同時にホウ酸を混合し、焼成温度を変化させた以外は実施例１と同様にして、マンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Example 2
Example 1 except that the type of manganese oxide was changed and boric acid was mixed simultaneously with Mn 3 O 4 particle powder, lithium carbonate, and aluminum hydroxide so as to have the composition shown in Table 1, and the firing temperature was changed. Similarly, lithium manganate particle powder was obtained.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

実施例２で得られたマンガン酸リチウム粒子を樹脂に混練してクロスセクションポリッシャーで粒子を切断し、その断面のＭｎ及びＡｌの分布状態をＥＰＭＡマッピングの結果から判断した。ＡｌがＭｎ同様に粒子断面で一様に分布していることが確認された。   The lithium manganate particles obtained in Example 2 were kneaded into a resin, the particles were cut with a cross section polisher, and the distribution state of Mn and Al in the cross section was judged from the result of EPMA mapping. It was confirmed that Al was uniformly distributed in the particle cross section like Mn.

実施例３〜５
Ｙ（Ａｌ、Ｍｇ）の種類、添加量及び焼成条件を種々変化させた以外は、前記実施例１と同様にしてマンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Examples 3-5
Lithium manganate particle powder was obtained in the same manner as in Example 1 except that the kind of Y (Al, Mg), the amount added, and the firing conditions were variously changed.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

比較例１
電解二酸化マンガン（ＭｎＯ２）（平均一次粒子径１５．１μｍ）、水酸化アルミニウム（Ａｌ（ＯＨ）３）及び炭酸リチウムを混合した後、９６０℃で焼成して、マンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Comparative Example 1
Electrolytic manganese dioxide (MnO 2 ) (average primary particle size 15.1 μm), aluminum hydroxide (Al (OH) 3 ) and lithium carbonate were mixed and then fired at 960 ° C. to obtain lithium manganate particle powder. .
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

比較例２
マンガン原料として、組成がＭｎ３Ｏ４であり、粒子形状は粒状であり、平均一次粒子径４．８μｍである酸化マンガン粒子粉末を用いた。 Comparative Example 2
As the manganese raw material, a manganese oxide particle powder having a composition of Mn 3 O 4 and a particle shape of granular and having an average primary particle diameter of 4.8 μm was used.

前記酸化マンガン粒子を含有する水懸濁液を、フィルタープレスを用いて５倍量の水で水洗を行った後、酸化マンガン粒子の濃度が１０ｗｔ％となるように邂逅した。この懸濁液に対して０．２ｍｏｌ／ｌのアルミン酸ナトリウム水溶液をＭｎ：Ａｌ＝９５：５となるように反応槽内に連続供給した。反応槽は攪拌機で常に攪拌を行いながら、同時に０．２ｍｏｌ／ｌの硫酸水溶液をｐＨ＝８±０．５となるように自動供給を行い、水酸化アルミニウムで被覆した酸化マンガン粒子を含む懸濁液を得た。
この懸濁液を、フィルタープレスを用いて酸化マンガン粒子の重量に対して１０倍の水により水洗を行った後、乾燥を行い、組成がＭｎ：Ａｌ＝９５：５であって平均二次粒子径が４．８μｍの水酸化アルミニウムで被覆された酸化マンガン粒子を得た。得られた酸化マンガン粒子の硫黄含有量は２３７ｐｐｍであった。 The aqueous suspension containing the manganese oxide particles was washed with 5 times the amount of water using a filter press, and then poured so that the concentration of the manganese oxide particles became 10 wt%. A 0.2 mol / l sodium aluminate aqueous solution was continuously supplied into the reaction tank so that Mn: Al = 95: 5. While the reaction vessel is constantly stirred with a stirrer, a 0.2 mol / l sulfuric acid aqueous solution is automatically supplied so that the pH becomes 8 ± 0.5, and the suspension contains manganese oxide particles coated with aluminum hydroxide. A liquid was obtained.
This suspension was washed with water 10 times the weight of the manganese oxide particles using a filter press, and then dried, and the composition was Mn: Al = 95: 5, and average secondary particles. Manganese oxide particles coated with aluminum hydroxide having a diameter of 4.8 μm were obtained. The obtained manganese oxide particles had a sulfur content of 237 ppm.

得られた水酸化アルミニウムで被覆したＭｎ３Ｏ４粒子粉末と炭酸リチウムとをＬｉ：Ｍｎ：Ａｌ＝１．０７２：１．８２８：０．１０の割合となるように１時間乾式混合し、混合物を得た。得られた混合物３０ｇをアルミナるつぼに入れ、９６０℃、空気雰囲気で３時間保持してマンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 The obtained Mn 3 O 4 particle powder coated with aluminum hydroxide and lithium carbonate were dry-mixed for 1 hour so that the ratio of Li: Mn: Al = 1.072: 1.828: 0.10 was obtained. Got. 30 g of the obtained mixture was put in an alumina crucible and kept at 960 ° C. in an air atmosphere for 3 hours to obtain lithium manganate particles.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

比較例３
表１に示す組成となるようにＭｎ３Ｏ４粒子粉末、炭酸リチウムと同時にホウ酸を混合した以外は比較例２と同様にして、マンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Comparative Example 3
Lithium manganate particle powder was obtained in the same manner as in Comparative Example 2 except that boric acid was mixed simultaneously with Mn 3 O 4 particle powder and lithium carbonate so as to have the composition shown in Table 1.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

比較例４
比較例２と同様にして、水酸化アルミニウムで被覆された酸化マンガン粒子を得た後、炭酸リチウム、酸化マグネシウムと混合して、焼成した。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Comparative Example 4
In the same manner as in Comparative Example 2, manganese oxide particles coated with aluminum hydroxide were obtained, mixed with lithium carbonate and magnesium oxide, and fired.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

比較例５
Ｍｎ化合物の種類、焼成条件を種々変化させた以外は、前記実施例１と同様にしてマンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Comparative Example 5
A lithium manganate particle powder was obtained in the same manner as in Example 1 except that the type of Mn compound and the firing conditions were variously changed.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

比較例６
用いるＹ（Ａｌ、Ｍｇ）元素化合物の平均二次粒子径（Ｄ５０）が実施例の８倍である８０μｍの原料を使用した以外は、前記実施例１と同様にしてマンガン酸リチウム粒子粉末を得た。
このときの製造条件を表１に、得られたマンガン酸リチウム粒子粉末の諸特性を表２に示す。 Comparative Example 6
A lithium manganate particle powder was prepared in the same manner as in Example 1 except that a raw material having an average secondary particle diameter (D 50 ) of Y (Al, Mg) element compound used was 80 μm, which was 8 times that of the Example. Obtained.
The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.

マンガン酸リチウム粒子粉末に硫黄分が残留することで、二次電池としたときにショートの原因や高温保存において不安定にさせる要因となることが考えられる。原因として、硫黄はマンガン酸化物とリチウム化合物とを混合し焼成するときに、リチウムと反応してＬｉ−Ｓ化合物として存在・残留することが考えられる。そのため、本来スピネルに入るべく存在していたＬｉ分が欠損してしまい、高温でのＭｎ溶出等高温特性を損ねると考えられる。   It can be considered that the sulfur content in the lithium manganate particle powder may cause a short circuit or cause instability in high temperature storage when a secondary battery is formed. As a cause, it is considered that sulfur is present and remains as a Li-S compound by reacting with lithium when manganese oxide and a lithium compound are mixed and fired. For this reason, it is considered that the Li component originally present to enter the spinel is lost, and high temperature characteristics such as Mn elution at high temperature are impaired.

本発明においては、マンガン酸リチウム粒子粉末の硫黄含有量を低減できたので、高温保存に優れた二次電池を得ることができる。   In the present invention, since the sulfur content of the lithium manganate particles can be reduced, a secondary battery excellent in high-temperature storage can be obtained.

本発明に係るマンガン酸リチウム粒子粉末は、硫黄含有量を低減できたので、出力特性が高く、高温保存特性に優れた二次電池用の正極活物質として好適である。
Since the lithium manganate particles according to the present invention can reduce the sulfur content, they are suitable as a positive electrode active material for secondary batteries having high output characteristics and excellent high-temperature storage characteristics.

Claims (7)

化学式１のマンガン酸リチウム粒子粉末において、硫黄含有量が１〜１００ｐｐｍであり、平均二次粒子径（Ｄ５０）が１μｍ〜１５μｍであり、且つ、該マンガン酸リチウム粒子粉末を正極活物質として用いた二次電池の電池測定において、高温サイクル維持率が９２％以上、容量回復率が９５％以上であることを特徴とするマンガン酸リチウム粒子粉末。
（化学式１）
Ｌｉ１＋ｘＭｎ２−ｘ−ｙＹｙＯ４＋ｚＡ
Ｙ＝Ａｌ、Ｍｇの少なくとも１種
Ａ＝融点が８５０℃以下である焼結助剤元素
（０．０３≦ｘ≦０．１５、０≦ｙ≦０．２０、ｚはＭｎに対して０〜２．５ｍｏｌ％） In the lithium manganate particle powder of Chemical Formula 1, the sulfur content is 1 to 100 ppm, the average secondary particle diameter (D 50 ) is 1 μm to 15 μm, and the lithium manganate particle powder is used as a positive electrode active material A lithium manganate particle powder having a high temperature cycle retention rate of 92% or more and a capacity recovery rate of 95% or more in the measurement of the secondary battery.
(Chemical formula 1)
Li 1 + x Mn 2-xy Y y O 4 + zA
Y = Al, at least one of Mg A = Sintering aid element having a melting point of 850 ° C. or lower (0.03 ≦ x ≦ 0.15, 0 ≦ y ≦ 0.20, z is 0 to Mn) 2.5 mol%) 格子定数が０．８１８〜０．８２２ｎｍである請求項１記載のマンガン酸リチウム粒子粉末。 The lithium manganate particle powder according to claim 1, having a lattice constant of 0.818 to 0.822 nm. 充放電容量を測定した場合に、初期の放電容量が８０ｍＡｈ／ｇ以上、１２０ｍＡｈ／ｇ以下である請求項１又は２に記載のマンガン酸リチウム粒子粉末。 3. The lithium manganate particle powder according to claim 1, wherein, when the charge / discharge capacity is measured, the initial discharge capacity is 80 mAh / g or more and 120 mAh / g or less. Ｍｎ３Ｏ４からなる酸化マンガン、Ｙ元素化合物及びリチウム化合物を混合し、８００℃〜１０５０℃で焼成することを特徴とする請求項１〜３のいずれかに記載のマンガン酸リチウム粒子粉末の製造方法。 Mn 3 O 4 made of manganese oxide, a mixture of Y element compound and a lithium compound, the production of lithium manganate particles according to any one of claims 1 to 3, characterized in that firing at 800 ° C. to 1050 ° C. Method. 請求項４記載のマンガン酸リチウム粒子粉末の製造方法において、酸化マンガンの硫黄含有量が１〜６０ｐｐｍであるマンガン酸リチウム粒子粉末の製造方法。 The method for producing lithium manganate particles according to claim 4, wherein the sulfur content of manganese oxide is 1 to 60 ppm. 請求項４記載のマンガン酸リチウム粒子粉末の製造方法において、酸化マンガンの平均一次粒子径が０．５μｍ以上であるマンガン酸リチウム粒子粉末の製造方法。 The method for producing lithium manganate particles according to claim 4, wherein the average primary particle diameter of manganese oxide is 0.5 µm or more. 請求項１〜３のいずれかに記載のマンガン酸リチウム粒子粉末を正極活物質またはその一部として用いた非水電解液二次電池。
The nonaqueous electrolyte secondary battery using the lithium manganate particle powder in any one of Claims 1-3 as a positive electrode active material or its part.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012212669A (en) * 2011-03-30 2012-11-01 Ngk Insulators Ltd Positive electrode active material powder for lithium secondary battery and lithium secondary battery
WO2013100070A1 (en) * 2011-12-27 2013-07-04 三井金属鉱業株式会社 Spinel-type lithium manganese transition metal oxide
WO2014077231A1 (en) * 2012-11-13 2014-05-22 戸田工業株式会社 Lithium-manganate-particle powder for use in non-aqueous electrolyte secondary battery, method for producing same, and non-aqueous electrolyte secondary battery

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102420326A (en) * 2011-11-25 2012-04-18 北京科技大学 Preparation method of bulky-grain spinel lithium manganate material
US9570741B2 (en) 2012-03-21 2017-02-14 Duracell U.S. Operations, Inc. Metal-doped nickel oxide active materials
US9028564B2 (en) 2012-03-21 2015-05-12 The Gillette Company Methods of making metal-doped nickel oxide active materials
KR101587209B1 (en) * 2013-03-26 2016-01-21 주식회사 엘앤에프신소재 Method for producing lithium manganate particle and nonaqueous electrolyte secondary battery
US9905851B2 (en) 2013-07-26 2018-02-27 Lg Chem, Ltd. Cathode active material and method of preparing the same
US9905850B2 (en) 2013-07-26 2018-02-27 Lg Chem, Ltd. Polycrystalline lithium manganese oxide particles, preparation method thereof, and cathode active material including the same
EP2918545B1 (en) * 2013-07-26 2016-11-23 LG Chem, Ltd. Polycrystalline lithium manganese oxide particles, method for preparing same, and anode active material containing polycrystalline lithium manganese oxide particles
CN105789568B (en) * 2014-12-16 2019-05-07 绍兴文理学院 A kind of doping element sulphur richness lithium lithium manganate material and preparation method thereof
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
CN108493443A (en) * 2018-03-09 2018-09-04 无锡晶石新型能源股份有限公司 A kind of technique that anode material for lithium-ion batteries is prepared based on manganese lithium
CN111362307B (en) * 2020-03-09 2023-11-14 福建省云智新材料科技有限公司 Preparation method of monocrystal lithium manganate positive electrode material for lithium ion battery
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CN113421998B (en) * 2021-06-21 2022-07-08 宁德新能源科技有限公司 Electrochemical device and electronic device
CN113603155B (en) * 2021-07-30 2023-01-10 蜂巢能源科技有限公司 Doping coating method, method for modifying ternary cathode material by adopting method and application

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10182159A (en) * 1996-12-18 1998-07-07 Tosoh Corp Lithium manganate and its production and lithium secondary battery using lithium manganate as anode
JPH11154512A (en) * 1997-11-21 1999-06-08 Asahi Chem Ind Co Ltd Nonaqueous electrolyte secondary battery
JP2000306577A (en) * 1999-02-15 2000-11-02 Denso Corp Positive electrode active material for nonaqueous electrolyte secondary battery, manufacture of the positive electrode active material and secondary battery using the positive electrode active material
JP2001143705A (en) * 1999-11-12 2001-05-25 Sanyo Electric Co Ltd Non-aqueous electrolyte secondary battery
JP2001216968A (en) * 2000-02-03 2001-08-10 Showa Denko Kk Positive electrode active material, its manufacturing method and nonaqueous secondary battery using the same
JP2002373655A (en) * 2001-06-18 2002-12-26 Shin Kobe Electric Mach Co Ltd Lithium secondary battery
JP2003157844A (en) * 2001-11-20 2003-05-30 Sagaken Chiiki Sangyo Shien Center Positive electrode active material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery
JP2004006247A (en) * 2002-03-26 2004-01-08 Shin Kobe Electric Mach Co Ltd Lithium secondary battery
JP2004292264A (en) * 2003-03-27 2004-10-21 Toda Kogyo Corp Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method
JP2005112711A (en) * 2003-12-24 2005-04-28 Mitsui Mining & Smelting Co Ltd Lithium-manganese-based compound oxide and lithium secondary battery
JP2006269106A (en) * 2005-03-22 2006-10-05 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19935090A1 (en) * 1999-07-27 2001-02-08 Emtec Magnetics Gmbh Lithium intercalation compounds containing lithium oxide
JP5199522B2 (en) 1999-08-17 2013-05-15 日揮触媒化成株式会社 Spinel-type lithium / manganese composite oxide, its production method and use
JP3900328B2 (en) 1999-11-12 2007-04-04 日本化学工業株式会社 Method for producing lithium manganese composite oxide
EP1142834A4 (en) * 1999-11-15 2009-06-17 Mitsubishi Chem Corp Lithium-manganese composite oxide, positive electrode material for lithium secondary cell, positive electrode and lithium secondary cell, and method for preparing lithium-manganese composite oxide
JP3456181B2 (en) * 1999-11-30 2003-10-14 日本電気株式会社 Lithium manganese composite oxide and non-aqueous electrolyte secondary battery using the same
JP2001283847A (en) * 2000-03-29 2001-10-12 Mitsubishi Electric Corp Manufacturing method of positive active material and positive active material as well as lithium secondary battery using same
US6699618B2 (en) * 2000-04-26 2004-03-02 Showa Denko K.K. Cathode electroactive material, production method therefor and secondary cell
JP2002198047A (en) 2000-12-27 2002-07-12 Shin Kobe Electric Mach Co Ltd Lithium secondary battery
JP4742866B2 (en) * 2003-05-26 2011-08-10 日本電気株式会社 Positive electrode active material for secondary battery, positive electrode for secondary battery, secondary battery, and method for producing positive electrode active material for secondary battery
JP5344111B2 (en) * 2007-03-30 2013-11-20 戸田工業株式会社 Method for producing lithium manganate for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
CN101855754B (en) * 2007-11-12 2013-07-03 户田工业株式会社 Lithium manganate particle powder for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery
EP2226293B1 (en) * 2007-12-28 2018-08-08 Toda Kogyo Corp. Lithium manganate for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery
KR101593725B1 (en) * 2008-09-18 2016-02-12 도다 고교 가부시끼가이샤 Method for producing lithium manganate particle powder and nonaqueous electrolyte secondary battery

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10182159A (en) * 1996-12-18 1998-07-07 Tosoh Corp Lithium manganate and its production and lithium secondary battery using lithium manganate as anode
JPH11154512A (en) * 1997-11-21 1999-06-08 Asahi Chem Ind Co Ltd Nonaqueous electrolyte secondary battery
JP2000306577A (en) * 1999-02-15 2000-11-02 Denso Corp Positive electrode active material for nonaqueous electrolyte secondary battery, manufacture of the positive electrode active material and secondary battery using the positive electrode active material
JP2001143705A (en) * 1999-11-12 2001-05-25 Sanyo Electric Co Ltd Non-aqueous electrolyte secondary battery
JP2001216968A (en) * 2000-02-03 2001-08-10 Showa Denko Kk Positive electrode active material, its manufacturing method and nonaqueous secondary battery using the same
JP2002373655A (en) * 2001-06-18 2002-12-26 Shin Kobe Electric Mach Co Ltd Lithium secondary battery
JP2003157844A (en) * 2001-11-20 2003-05-30 Sagaken Chiiki Sangyo Shien Center Positive electrode active material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery
JP2004006247A (en) * 2002-03-26 2004-01-08 Shin Kobe Electric Mach Co Ltd Lithium secondary battery
JP2004292264A (en) * 2003-03-27 2004-10-21 Toda Kogyo Corp Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method
JP2005112711A (en) * 2003-12-24 2005-04-28 Mitsui Mining & Smelting Co Ltd Lithium-manganese-based compound oxide and lithium secondary battery
JP2006269106A (en) * 2005-03-22 2006-10-05 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012212669A (en) * 2011-03-30 2012-11-01 Ngk Insulators Ltd Positive electrode active material powder for lithium secondary battery and lithium secondary battery
WO2013100070A1 (en) * 2011-12-27 2013-07-04 三井金属鉱業株式会社 Spinel-type lithium manganese transition metal oxide
KR20140112044A (en) * 2011-12-27 2014-09-22 미쓰이금속광업주식회사 Spinel-type lithium manganese transition metal oxide
GB2514021A (en) * 2011-12-27 2014-11-12 Mitsui Mining & Smelting Co Spinel-type lithium manganese transition metal oxide
JPWO2013100070A1 (en) * 2011-12-27 2015-05-11 三井金属鉱業株式会社 Spinel type lithium manganese transition metal oxide
KR101637410B1 (en) 2011-12-27 2016-07-07 미쓰이금속광업주식회사 Spinel-type lithium manganese transition metal oxide
US9893355B2 (en) 2011-12-27 2018-02-13 Mitsui Mining & Smelting Co., Ltd. Spinel-type lithium manganese transition metal oxide
WO2014077231A1 (en) * 2012-11-13 2014-05-22 戸田工業株式会社 Lithium-manganate-particle powder for use in non-aqueous electrolyte secondary battery, method for producing same, and non-aqueous electrolyte secondary battery
JPWO2014077231A1 (en) * 2012-11-13 2017-01-05 戸田工業株式会社 Non-aqueous electrolyte secondary battery lithium manganate particle powder, method for producing the same, and non-aqueous electrolyte secondary battery

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